Production of vinyl fluoride and/or 1,1-difluoroethane



United States Patent Olfice 3,541,166 Patented Nov. 17, 1970 3,541,166 PRODUCTION OF VINYL FLUORIDE AND/R 1,1-DIFLUOROETHANE Hiroyuki Wada, Kyoto-fu, and Yasumasa Kawakami, Osaka-fu, Japan, assignors to Daikin Kogyo Co., Ltd., Osaka-tn, Japan, a corporation of Japan No Drawing. Filed May 21, 1968, Ser. No. 730,949 Claims priority, application Japan, May 24, 1967, 42/ 32,979 Int. Cl. C07c 17/08 US. Cl. 260--653.4 4 Claims ABSTRACT OF THE DISCLOSURE wherein Y is the molar ratio of vinyl fluoride yield to feed acetylene, F is the molar ratio of feed hydrogen fluoride to feed acetylene, V is the molar ratio of additive vinyl fluoride to feed acetylene, R is the molar ratio of additive 1,1-difluoroethane to feed acetylene, P is the reaction pressure (absolute pressure), A is the molar ratio of an inert gas to feed acetylene and B is the value calculated from the following formula:

in which T is the reaction temperature, F plus Y being larger than 2, to produce vinyl fluoride and/or 1,1-difluoroethane in an optional proportion.

The present invention relates to the production of vinyl fluoride and/ or 1,1-difluoroethane.

It is known that the reaction of acetylene with hydrogen fluoride in the vapor phase in the presence of a variety of solid catalysts yields vinyl fluoride and/or 1,1-difluoroethane. It is also known that vinyl fluoride and 1,1-difluoroethane are useful respectively as the starting monomer for the production of polyvinyl fluoride and as a refrigerant or the starting compound for the preparation of vinylidene fluoride. Therefore, it is highly advantageous to be able to produce vinyl fluoride and/or 1,1-difluoroethane in an optional proportion as desired with a high conversion of acetylene in the above reaction. Although there have been proposed a number of procedures utilizing the said reaction, all these are directed to either increasing the conversion of acetylene or improving the yield of vinyl fluoride oi" 1,1-difluoroethane. Thus, none of the known procedures can realize the said advantageous production according to the present invention.

The object of the present invention is to provide a process for preparing vinyl fluoride and/or 1,1-diffuoroethane in an optional proportion from acetylene and hydrogen fluoride with a high conversion of acetylene.

According to the present invention, the reaction between acetylene and hydrogen fluoride is carried out by introducing into the reaction zone in the presence of a catalyst these feed materials with at least one of the additive materials, i.e. vinyl fluoride and 1,1-difluoroethane, under the conditions substantially satisfying the relationship of the following equation:

wherein Y is the molar ratio of vinyl fluoride yield to feed acetylene, F is the molar ratio of feed hydrogen fluoride to feed acetylene, V is the molar ratio of additive vinyl fluoride to feed acetylene, R is the molar ratio of additive 1,1-difluoroethane to feed acetylene, P is the reaction pressure (absolute pressure), A is the molar ratio of an inert gas to feed acetylene and B is the value calculated from the following formula:

.Lxloll B=2.79 10 1.43 10 in which T is the reaction temperature, F plus Y being larger than 2.

When vinyl fluoride or 1,1-difluoroethane is used alone as the additive, R or V is zero. Thus, the Equation 1 in such case may be written as follows:

wherein the symbols are each as defined above.

In determining the actual reaction conditions, Y is first determined to a desired value. Then, five factors optionally selected from F, V, R, P, A and T are appropriately determined to satisfy the said conditions. Lastly, the remaining factor is calculated according to the Equation 1 or, when R or V is zero, according to the Equation 2 or 3.

Instead of the molar ratio Y of vinyl fluoride yield to feed acetylene, the molar ratio of l,l-difluoroethane yield to feed acetylene may be determined to a desired value. In such case, the relationship of the following equation:

wherein X is the molar ratio of 1,1-difluoroethane yield to feed acetylene and Y is as defined above should be satisfied.

The amount of feed hydrogen fluoride should be from 1 to 4 mols per 1 mol of feed acetylene. The smaller proportion of hydrogen fluoride results in marked decrease of the conversion of acetylene, while the larger proportion will reduce the utilization of hydrogen fluoride.

The respective amount of additive vinyl fluoride and/ or 1,1-difluoroethane should be in the range of 0.05 to 8 mol per 1 mol of feed acetylene. When the rate of the additive(s) exceeds the upper limit, the amount of the reaction gas to be treated increases so that the production efliciency of the reactor decreases.

The maintenance of the reaction temperature (T) at 200 to 320 C. (preferably 220 to 300 C.) is essential for carrying out the reaction practically and efliciently. When the temperature is below 200 C., the reaction rate is too small. When ti is above 320 C. the decomposition of acetylene occurs to produce undesirable byproducts such as ethylene.

The reaction pressure (P) may be from 0.5 to 4 atm., preferably about atmospheric pressure. Lower pressures render the operation difficult, whereas higher pressures cause explosion of acetylene.

The contact time may be appropriately selected depending on the reaction conditions. In the space velocity of feed acetylene (at the normal state), it may be from 1 to 1000 ml./hour per 1 g. of the catalyst.

The catalyst may be a per se conventional one insofar as having a high catalytic activity. Specific examples include aluminum fluoride, aluminum oxide and their mixtures [U.S. patent 2,471,525, French patent 1,325,750], aluminum oxide-zinc fluoride mixture [U.S. patent 2,574,- 480], zinc compounds treated with hydrogen fluoride in nitrogen at 65 to 200 C. [U.S. patent 2,716,142] and chromium oxides and salts [US patent 2,892,000]. Of these, aluminum fluoride is the presently-preferred one.

When an inert gas such as nitrogen is incorporated into the feed materials, it serves for the prevention of superheating and control of the temperature at the reaction zone. However, such addition is not essential for the successful accomplishment of the present invention,

For carrying out the reaction, the feed materials with process of this invention is advantageous in yielding continuously vinyl fluoride and/or 1,1-difluoroethane in an optional proportion with a high conversion of acetylene, compared with the known procedures.

Presently-preferred embodiments of this invention are illustratively shown in the following examples.

EXAMPLE 1 In a vertically mounted tubular stainless steel reactor (inside diameter, 27 mm.; length, 600 mm.), aluminum fluoride catalyst (120 g.) in pellet form was placed, and the reactor was heated in a molten salt bath. A mixture of acetylene, anhydrous hydrogen fluoride and vinyl fluoride was passed into the top of the reactor at almost atmospheric pressure. The effluent product from the bottom of the reactor was scrubbed with water and aqueous alkali to remove hydrogen fluoride, taken in a sampling bottle and analyzed by gas chromatography. The vinyl fluoride, 1,1-difluoroethane, hydrogen fluoride and acetylene may also be separated by distillation if desired.

The results are shown in Table l as well as the predetermined molar ratio Y of vinyl fluoride yield to feed acetylene and the reaction conditions. In the reaction conditions, two of the factors temperature (T), molar ratio of feed hydrogen fluoride (F) to feed acetylene and molar ratio of additive vinyl fluoride (V) to feed acetylene as underlined in the table were first selected and then the remaining factor was determined according to the said Equation 1 in which the pressure (P) was set at 1 atm.

From the table, it can be seen that the molar ratio Y of vinyl fluoride yield to feed acetylene as found is nearly equal to that previously determined.

TABLE 1 Reaction conditions Results Prede- Molar ratio of iced materials Space Veloc- Convcr- Composition of ctIluent product tel-mined 'l nmvrnity of 11 slOfll 1101 p r en h on 111 t 4 'l n. .cat- 0 2 2 a iiliionl a F 2 c (V) aly gtlhiz) (percent) CH2 OIII CIL-iCH 2 2 Cal-I4 ratio 1 0 1 3. 01 23 2'5 70 09. 8 l8. 81. Z 0. 2 0. 1 0, 01 0. 1 2. 30 44 307 135 90. 8 70. 29. 0 0. 1 (p) O 29 0. 10 1 2. 08 0. 46 286 122 00. 5 36. 0 (i3. 1 0. 3 (3) 0, 08

1 CHQ=CIIFIGQHZ (Y). 2 Trace.

EXAMPLE 2 the additive material(s) in the vapor phase are passed into a conventional reactor where the catalyst is charged under the reaction conditions explained above. The reactor is required to be made of a material which is resistant to hydrogen fluoride at the reaction temperature employed and which does not react with acetylene to form explosive acetylide and is, for example, stainless steel, nickel or Inconel. An example of the preferred type of reactor is a vertically mounted tubular stainless steel reactor heated electrically from the outside, into which the catalyst is charged in pellet form.

In the reaction, it is noted that the amount of vinyl fluoride and/or 1,1-difluoroethane initially incorporated remains substantially unchanged. Namely, the subtraction of the amount of the vinyl fluoride originating in the feed acetylene from that of the vinyl fluoride existing in the efliuent product results in a value substantially equal to the amount of the initially incorporated vinyl fluoride. The same thing is true for 1,1difluoroethane. Therefore, a suitable amount of the vinyl fluoride and/or 1,1-difluoroethane separated from the eflluent product may be recycled into the reactor for the continuous production of vinyl fluoride and/or 1,1-difluoroethane. In other words, the materials which are consumed in the reaction are only acetylene and hydrogen fluoride, and the successive provision of these feed materials in a constant ratio into the reactor makes it possible to produce continuously vinyl fluoride and/or 1,1-difluoroethane in an optional ratio as previously determined without manufacturing separately the additive materials and supplying them into the reaction system.

As will be understood from the above description, the

Using the same reactor and catalyst (200 g.) as in Example 1, acetylene and hydrogen fluoride were reacted. Into the reaction zone, a mixture of acetylene, hydrogen fluoride and vinyl fluoride was introduced. The eflluent product from the reactor was scrubbed with water and aqueous alkali and introduced into a condenser to separate vinyl fluoride. The separated vinyl fluoride was supplied to the reactor for continuous carrying out of the reaction.

According to the said Equation 1 in which the molar ratio Y of vinyl fluoride yield to feed acetylene was selected as zero (i.e. the yield percent of 1,1-difluoroethane being the temperature (T) as 263 C. and the molar ratio of feed hydrogen fluoride (F) to feed acetylene as 2.50, the molar ratio of additive vinyl fluoride (V) to feed acetylene was determined as 0.30.

Under the above chosen reaction conditions, the reaction was continuously eflected using a total of 424 g. of acetylene (calculated from the flow rate and time) at a space velocity of 75.1 ml./g. catalyst/hour for 25 hours to give 99.6% conversion of acetylene. At the stationary state, the efiluent product was sampled and analyzed by gas chromatography, and the molar ratio of vinyl fluoride yield to feed acetylene was found to be 0.03. The yield of 1,1-difluoroethane was 990 g.

The feed materials contained 100 g. of vinyl fluoride initially and, with the proceeding of the reaction, the vinyl fluoride recovered from the eflluent product was recycled into the reaction zone to leave finally 97 g. in the reaction system. Thus, no material increase or decrease was found in the amount of vinyl fluoride present during the reaction.

EXAMPLE 3 Using the same reactor and catalyst (120 g.) as in Example 1, acetylene and hydrogen fluoride were reacted. Into the reaction zone, a mixture of acetylene, hydrogen reaction conditions, of which the molar ratio of feed hydrogen fluoride (F) to feed acetylene was determined according to the said Equation 1 by incorporating the values of the other factors therein.

fluoride and 1,1-difluoroethane was introduced. The ef- TABLE 3 fluent product from the reactor was scrubbed with Water Number and aqueous alkali, taken in a sampling bottle and ana- 1 2 lyled y a gas chromatography- Predetermined molar ratio, CH2=OHF/C2H2(Y) 0.7 0.2

The results are shown in Table 2 as well as the previ- Reaction conditions, ously determined molar ratio Y of vinyl fluoride yield to rHatiO Offeed materials! 1 feed acetylene and the reaction conditions. In the reac- 78 5511111: j 1 L9 tion conditions, two of the factors temperature (T), 5 99 54,? 8-; 8- molar ratio of feed hydrogen fluoride (F) to feed acetylem sttu coy'z f j one and molar ratio of additive 1,1-difluoroethane (R) Yessure 1 1 to feed acetylene as underlined in the table were first ffg i i 193 chosen and then the remaining factor was determined aciq m 6 2 2 Percent 8 cording to the said Equation 1 in which the pressure (P) Composltm ofemuent product (molpemen 44.2 52.5 was set at 1 atm. 3-; 5-:

From the table, it can be seen that the molar ratio Y of {1 '1 vinyl fluoride yield to feed acetylene as found is nearly Found molar ratio, OH2=CHF/C2H2(Y) 0.696 0.198 equal to that previously determined. Irace.

TABLE 2 Reaction conditions Results Molar ratio of feed materials Space veloc- Qonver- Composition of efliuent product Selected Temperaity of 02112 sufnbra te (moi percent) No 1 3 9 C2112 HF (F) CHaCHFZ (R) perc en t; CHFOHF CH3OHF2 02H; 02H, ratio 1 1 0.15 1 2.80 0.90 238 70 99.8 8.0 91.9 0.1 0.152 2 1. 00 1 '1. 25 1.22 20 153 99.5 44.3 55.0 0.2 0. 004 3 0.50 1 2'99 0. 31 20 2 220 99.8 23.4 71.5 0.1 0. 514 4 0.50 1 270 073 2 280 220 99.3 37.1 02.3 0.5 0.1 0. 405 5 0.10 1 271 0.5 2720 23 99.0 5.7 91.1 .2 0,10 0 0.50 1 '70 0?) E50 57 99.7 33.2 00.4 0.3 0.1 0. 49s 7 1.00 1 3.33 31 06 "2% 45 99.0 25.5 74.2 0.1 0.2 1.02 8 1 2, "'6 E52 220 99.7 27.0 71.1 0.3 1.0 0.271

1 CH2=OHFIC2H2 (Y). Trace.

EXAMPLE 4 EXAMPLE 6 Using the same reactor and catalyst (130 g.) as in Using the same reactor and catalyst (400 g.) as in Example 1, acetylene and hydrogen fluoride were re- 40 Example 1, acetylene and hydrogen fluoride were reacted. acted. Into the reaction zone, a mixture of acetylene, Into the reaction zone, a mixture of acetylene, hydrogen hydrogen fluoride and 1,1difluoroethane was introduced. fluoride, vinyl fluoride, 1,1-difluoroethane and nitrogen The efliuent product from the reactor was scrubbed with was introduced. The results are shown in Table 4 as water and aqueous alkali and introduced into a conwell as the reaction conditions, of whichthe temperdenser to separate 1,1-difluoroethane. The separated 1,1- ature (T) was determined according to the said Equation difluoroethane was supplied to the reactor for continuous 1 by incorporating the values of the other factors therein. carrying out of the reaction.

According to the said Equation 1 in which the molar TABLE 4 ratio Y of vinyl fluoride yield to feed acetylene was Predelelmmedmolar Yatlo 2= 2 2 selected as 1.0, the temperature (T) as 270' C. and the Reactlon condlflonsi molar ratio of feed hydrogen fluoride (F) to feed acetyl- Molar Tatlo of feed materlals! one as 2.10, the molar ratio of additive 1,1-difluoroethane z z 1 (R) to feed acetylene was determined as 2.22. HF

Under the above chosen reaction conditions, the re 3 2 action was continuously eflected using a total of 282 g. 2= of acetylene (calculated from the flow rate and time) at N2 a space velocity of 55.3 mg./ g. catalyst/hour for 20 hours Temperature 225 to give 99.3% conversion of acetylene. At the stationary Pressure (aPsolute) (kg/P1112) state, the efliuent product was sampled and analyzed by Space veloclty of C2H2(m1l-/gcatalyst/hr) 75 means of gas chromatography, and the molar ratio of Results: vinyl fluoride yield to feed acetylene was found to be E P rate of CZHZ (Percent) 0.973. The yield of vinyl fluoride was 460 g. Composmon of effluent Product (H101 P The feed materials contained 350 g. of 1,l-difluorocent): ethane initially and, with the proceeding of the reaction, CH2=CHF the 1,1-difluoroethane recovered from the effluent prod- 5 CHBOHFa uct was recycled into the reaction zone to leave finally C2H2 366 g. in the reaction system. Thus, no material increase C2H4 g: or decrease was found in th 2 during the reaction. 6 amount of 1 1 dlfluoroethane Found molar ratio CH =CHF/C H (Y) 0.710

- EXAMPLE 5 What is claimed is:

U i h Same reactor d Catalyst 100 as i 1. In the production of vinyl fluoride or 1,1-difluoro- Example 1, acetylene and hydrogen fluoride were reacted. ethane y reacting acetylene with hydrogen fluoride in Into the reaction zone, a mixture of acetylene, hydrogen the vapor Phase in the P193611:e of a Catalyst known to fluoride, vinyl fluoride and 1,1-di'fluoroethane was introcatalyze such reaction, the method which comprises introducing acetylene and hydrogen fluoride with at least duced. The results are shown in Table 3 as well as the one of vinyl fluoride and 1,1-difluroethane into the reaction zone of a reactor under conditions substantially satisfying the relationship of the following equation:

wherein Y is the molar ratio of vinyl fluoride yield to feed acetylene, F is the molar ratio of feed hydrogen fiuoride to feed acetylene in the range of 1 to 4, V is the molar ratio of additive vinyl fluoride to feed acetylene in the range of 0.05 to 8, 'R is the molar ratio of additive 1,1-difiuoroethane to feed acetylene in the range of 0.05 to 8, P is the absolute reaction pressure, A is the molar ratio of an inert gas to feed acetylene and B is the value calculated from the following formula:

in which T is the reaction temperature between 200 and 320 C., F plus Y being larger than 2, to produce vinyl fluoride or 1,1-difluoroethane in a predetermined propor- Hon.

2. The method according to claim 1, wherein R is zero, the reaction being carried out under the conditions substantially satisfying the relationship of the following equation:

wherein Y is the molar ratio of vinyl fluoride yield to feed acetylene, F is the molar ratio of feed hydrogen fluoride to feed acetylene in the range of 1 to 4, V is the molar ratio of additive vinyl fluoride to feed acetylene in the range of 0.05 to 8, P is the absolute reaction pressure, A is the molar ratio of an inert gas to feed acetylene and B is the value calculated from the following formula:

wherein Y is the molar ratio of vinyl fluoride yield to feed acetylene, F is the molar ratio of feed hydrogen fluoride to feed acetylene in the range of l to 4, R is the molar ratio of additive 1,1-difluoroethane to feed acetylene in the range of 0.05 to 8, P is the absolute reaction pressure, A is the molar ratio of an inert gas to feed acetylene and B is the value calculated from the following formula:

in which T is the reaction temperature between 200 and 320 C., F plus Y being larger than 2, to produce vinyl fluoride or 1,1-difluoroethane in a predetermined proportion.

4. The method according to claim 1, wherein the solid catalyst is aluminum fluoride.

References Cited UNITED STATES PATENTS 2,892,000 6/1959 Skiles 260-653.4

DANIEL D. HORWITZ, Primary Examiner US. Cl. X.R. 260653.6 

